Spray material and method of making the same



Patented Mar. 7,1944

" 1 UNITED: STATES PATENT OFFICE SPRAY MATERIAL AND METHOD OF MAKIJIGTHE SAME I Robert B. Arnold, stonewallcourts, Va, assignor to TobaccoBy-Products and Chemical Corporation, Louisville, Ky., a corporation ofDelaware .No Drawing. Application July 17, 1940,

- Serial No. 345,985

11 Claims. (011167-33) than has heretofore'been attained in acombination-spray material, the alkaloid being in such forms thatthesp'ray made from such spray material may have not'only a strongcontact action, due to a high percentage 01' a portion of the alkaloidwhich is water-soluble, but also a strong 15 action as a stomach poison,due to a high percentage of a portion of the alkaloid which iswater-insoluble and durable, while at the same time the said spraymaterial is very readily and quickly wetted by and finely dispersed inwater, a the alkaloid or at least not to any appreciable yet'is sodurable that it may be stored and shipped in ordinary, that is to say,non-hermetically sealed containers, without loss of alkaloid due todecomposition or oxidation even when kept for a relatively long time.

A further object of the invention is provide a spray material having thecharacteristics above described which will be compatible with the usualfungicide sprays ,of the non-alkaline sulphur and copper types and withthe so-called summer oil lnsecticidal sprays. In fact. the spraymaterial of the present invention is compatible with any otherspray'material that does not give an appre-' ciable, alkaline reactionin the water of the spray tank.

By -the provision of a dry concentrated parasiticidal spray material ofthe type described, the cost of packaging.- shipping and storing thematerial is greatly reduced, which becomes particularly important'at'the present time due to the general long distance transportation ofsuch spray materials, including transportation to foreisn countries,

With the above objects in view a product e'mbodying the invention,broadly considered, comprises an alkaloidal insecticidal materialselected from the group consistum of nicotine, nornico-l tine,anabasine, part of which alkaloid is chemically combined with acomminuted, solid baseexchange material 'to. form 'an insolublenonvolatile insecticide, and the remainder of which alkaloid,constituting an essential portion of the whole amount of alkaloid, iscombined with an acid to form a water-soluble salt, this watersolublesalt being carried and-retainedby asuit- I able solid carrier, and beingeither a strong mono-basic inorganic acid salt of said alkaloid,

which salts firmly retain the acid against volatilization, or apoly-basic acid salt of such an alkaloid, from which a part of thealkaloid is readily volatilized, associated with a volatilize.- tionpreventer to form a non-volatile but watersoluble compound or thealkaloid.

In one embodiment of the invention, the only carrier of the solublealkaloid salt is the same material, namely, the solid base-exchangematerlal, which holds some of the alkaloid in chemical combination.

In another embodiment of the invention, the chemically combined alkaloidis carried by a solid base-exchange material, as hereinbefore re-'ferred to, while the, excess alkaloid in watersoluble salt form iscarried, in part, by said baseexchange material and in part by anothermaterial not capable of chemically combining with extent, so that it maybe termed chemically inert to the alkaloid, but-having goodadsorptivepowers tor adsorbing the particular alkaloid used with it,thisrchemically inert material which carries excess alkaloid beingintimately compounded with the solid base-exchange material which hasthe alkaloid in chemical combination. The said other chemically inertmaterial may be a clay,

oi sucha type that it will not react chemically with the alkaloid salt,or at least to a lesser extent than does the base-exchange material.

"With this particular mixture of solid basedirectly. However, it hasbeen found that a more generally applicable insecticide will be obtainedii a partly volatile salt oi the alkaloid, that is to say, a salt oi. apoly-basic acid be used, in which case there is employed a component forpreventing escape of nicotine from the spray composition. This may betermed a fixing component and must be distinguished from a mere retarderwhich is intended to insure a slow delivery of nicotine on the plant.Thisfixing component mingles not only with the part of the exgess saltoi the alkaloid on the clay but also ,with that part carried by thebase-exchange material having alkaloid in chemical combination,

. thereby avoiding any possibility of evolution ofvolatile alkaloid, andat the same time providing a substantially dry product which can bereadily handled and packaged The invention also includes a processormaking the insecticidal spray material, which process, generallyconsidered, comprises, as a most essential Q featilre, "contacting abase xchange material having the capacity of entering into abase-exchange reaction with a salt of an inbe found in the general classof rawmaterials known as bentonites, which class, however, in-

cludes some materials not so satisfactory for applicants purpose. It hasbeen found that certain Wyoming bentonites known on the market 'asvdltla wilk ii tegand g'somel" Qaliforn'ia museums-shown as Filtrol andstay-up are secflcidl alkaloid of the pe hereinbefore set:

forth, with such a salt of thegalkaloid in t presence oi.a restrictedamount of water,I the.; g

proportion of the alkaloid salt being always considerably in excess ofthe amoumneesary supply the alkaloid which tintersl iiitdlhiSd-efichange reaction with the base-exchange m'ate-' riaLwhereby an excess thealkaloid salt unacted upon by the base-exchange inaterial is w provided.

It will be understood from the description ,oi

the product hereinabove given-that when a polybasic acid salt of thealkaloid is used, the process further includes the step of adding 'andthoroughly incorporating a, small proportion of a fixing component"which will substantially inhibit the volatilization witirtime ofithatpart of the alkaloid contained in' the excess of a1 kaloid saltwhichnormally volatilizesu This makes it possible to store and ship thefinalproduct' withoutany orany appreciable loss of insecticidal value.While several types or solid base-exchange materials are suitable foruse in producing a dry.

insoluble salt of the hereinbeforementioned.

alkaloids, it has been'found that certain solid, inorganic base-exchangematerials which are complex polysilicateshave' the great advantage thatthey quickly react with the alkaloids named to form a stable; complexpolysilicatebi the alkaloid; and furthermore such complex'polysilicatesare low in cost and readily obtained in large quantities" Hence, in thedescription'hereina fter, reference will be made only to the complexpolysilicates having base-exchange properties, it [being understood,-however; that other base-exchange material may be employed.

In one form or. the invention a, complex poly- .silicate-having therequired. base-exchange prop- 'erties is used as the only carrier of theexcess alkaloid salt of a polybasic acid and of. the fixing. agent, sothat aft r incorporation ofthe alkaloid excellent for carrying out thepresent invention.

These satisfactory bentonite's may be classified exchange properties.(Sometimes the aluminum as complexspoly-alumino-silicates having baseisreplaced in part by iron in trivalent iorm.)

Such silicates hold in combination divalent "land monovalent metals, forexample, calcium,

magnesiumfsojdii m and sometimes potassium. and in general the alkaloidreplaces part of such divalent -or moncvalent metals in the base-ex--change reaction and thereby enters into chemical combination with thepoly-alumino- (or ierroor alumino ferro) silicate.

:iv *When usinguthe best. types of-com'plexpolysilicates abovementioned; to dorm a. chemical combination with thevalkaloid iselected,ltiwill he found --that' the .resultant product gives a durable alkaloidcombination vfromwhich the chemically-combinedalkaloid-will not bedissolved out bywater snor' will .-the alkaloid,-i.such as asine,. mayhex-em loyed, uin usual :practice the nicotine salts; areemployed, and,of these, jnicctine sulphate is'more readily available; but

"' firming-the salt of ,a dibasic acid,--a partof. its

salt, the Veryrestrictedamountot .waten and the small percentage-offixing agent, the :re-

.sultingproduct is then subjected to heat at least sufficient to- -dryit; is ground-and graded and .the liner. material is readydorpacka'gingand shipment to. the consumer.

.--,In another form of the invention, tarsus :mixed with a complexpolysilicate an additional finely comminuted carrier which may be termedsubstantiallyinert to the alkaloid. salt and serves chieflyv asanadsorbent to-hold-at least a large part of the excess alkaloid salt..In this case,-if

poly-basic acidsalt is used'with a fixing agent, the latter unites withthat ..-part of .the excess alkaloid salt carried by the inert carrier.as well as with that partof said excess salt carried by thecomplex-polysilicate'itself, The resulting product or this modifiedprocess is;-also subjected to heat to dry itpis ground andgraded and the.flner product is then ready for. storage andshipmentasasprayumaterialaV I The complex polysilicate whichhas base-exchange properties andwhichis particularly suit-' able for r g out the present inventionmay te n sacid may v yfro whole material. 1,. t

alkaloid maybe set free easily and hence may he said to be volatile inpart-.=- As a non-volatile nicotine. salt, nicotme-zincehydrochloridehas been found to be suitable, but only for certain purposes, where theplant to besprayed will not ei lured by t e z y -the purposeofpreventing the release of nicotine- .from the, spray -composltionapplicant has found that-a, small,;percentage of tannic acid iar lessthan would be sumcientto combine lwithiall the volatilizable portion of,thenicotine in.the;water-=sqluble salt, will serve asa fixing componentif, thoroughly commingled. with =.the water-soluble salt during themanufacture ofthe spraymaterial. In general, the percentage of 5%; to 1(l% oi the .1... 6P7? X :1- A, :I' Applicant has discoveredqthat anothervery-ad- ,vantageousiixingicomponent is the dust made fromflue-curedtobacco. -such a tobaccodust is ,acidbut its acidity is thatdue tov anorganic. acid weaker than the acid of the water-solublenicotine salt. and hence iszunable to act ,chemical1y thereon. It is not,-pos sible touuse. an alkaline tobacco \dust as that-will} combine w tthe acid of the water-solublesalt and set free d preportional amount,ofv nicotine 'Aitobacco dust which is neutral and. .will remain so, maybe used, but in practice it is saier touse the flue cured tobacco dustas,,that has and retains a pronounced acidity.,.,Sucha' dust should hein s h r p i at it wilifo 'mi qm'a i 20% to about loat e mixture.

The percentage 3 of{moisturelpresent finijthg satisfactory forapplicant's purpose.

now be set forth:

It has been found that thetobacco dust, neu-' tral or acid, has theadditional advantage that it aids in carrying out the process, by actingin part as an adsorbent of some of the watersoluble nicotine salt and atthe same time tends to overcome or at least reduce caking of the complexpolysilicate salt of nicotine duringthe drying operation.

Applicant has further discovered that certain mineral lubricating oilswhich have a boiling point of above about 700 F.' and a viscosity ofbetween 180 and 900 seconds Saybolt at 100 F.

are particularly suitable as a fixing component if care is taken to useonly a small proportion of such oil, most advantageously about and in nocase less than about 2% or more than 8%.

Red engine oil has been used with success.

If too much is used thespray composition will not be wetted well by thewater when mixed in the spray tank. It has been found that 5% of thesaid oil does not injuriously affect the wetting properties ,of thespray composition, and such an oil has the additional advantage that,with a .complex polysilicate salt of nicotine, it serves as a sticker,that is, it increases the adhesion of the said salt to the leaves of thesprayed plant, so that the latter is not so easily washed off the plantby rain. When used with the complex polysilicate it is readily adsorbedand absorbed by the latter, so that the resultant spray material is lesslikely to cake in the drier, the dried product is more easily ground tofine dust and caking during storage and transit in avoided. At the sametime there is no chance of leakage of oil from the spray composition.The latter, when containing said mineral lubricating oil as a fixingcomponent has a velvety feel.

Another fixing component which may be used iroleic acid and this is t6be used in about the same proportions as the mineral lubricating oilhereinbefore discussed, viz: from 2 to 8 percent.

In that modification of the invention in which there is added aso-called inert carrier to carry by adsorption some of the excessalkaloid salt,

it has been found advantageous to employ as a .carrier certain selectedclays which will have no, or but little, chemical reaction with thealkaloid salt employed. Some clays, such as pure kaolin,

have some appreciablebase-exchange properties and, hence, whenrusingpure kaolin, allowance should be made for the increase in fixed alkaloiddue'to the use of such kaolin. other clays which are not so pure askaolin have little or no baseexchange action and are very satisfactoryfor applicants process. Hence, it is well in selecting a commercial clayfor use as an inert carrier to make a proper test of the clay in advanceof its use. In this form of the invention, by properly proportioning theamount of inert carrier, such as clay, to the amount of the complexpolysilicate base-exchange material, the ratio of fixed alkaloid tosoluble alkaloid may be correspondingly adjusted. In practice it hasbeen found that certain clays on the market known as Bancroft clay andInert C from Georgia are entirel Some specific examples of the inventionwill Example I A suitable bentonite having the required charac eristicshereinbefore pointed out is suitably tage of lubricating oil.

comminuted and graded, as by sifting, to remove all particles which willnot pass a screen,

sulphate of 40% nicotine strength and containing about 40% water isadded in considerable excess, and also there is added a lubricating oilhaving a viscosity at F. of between 190 and 900 seconds Saybolt, the oilnot to be less than 2% and not to exceed about 5% or 6% of the total dryweight of all the material. The lubricating all known as Red engine oilhas been found very suitable. After thoroughly mixing the materials, asby vigorous stirring for 10 or 15 minutes in a suitable paddle mixer,the resultant product is not a wet slurry but only a slightly damp,finely comminuted material, readily handled by conveyors or chutes. Thisproduct is passed into a dryer kept at a temperature of about to 220 F.and retained in such dryer until substantially all the free moisturecontained in the bentonite and in the nicotine sulphate has been drivenoil. In usual practice a rotary steam dryer is employed, the length andslope being such that the product discharged is dry. The resultantproduct is then ground and graded, as by air-separation or sifting so asto obtain a fine product, which constitutes the desired spray material.The relative proportions by weight of the materials at the beginning andat the end'oi' the process are as follows:

It will be seen that the water present in the raw mix is about 16%. Thefinished spray material will contain about 14.8% =nicotine, of whichabout 50% is chemically combined with the bentonite and the remainder isin the form of nicotine sulphate which, with the lubricating oil as afixing component, is adsorbed by the nicotine-bentonite salt. Astheexqess nicotine sulphate loses its water. during the dryingoperation, it gradually passes into the form of a Jelly, adheres to andis adsorbed by the particles of nicotine-bentonite powder, and assistsin holding the small percen- The spray? material in its finished form isa finely comminuted dry product, with a velvety feel due to the presenceof the slight amount of oil. It can be readily poured into suitablepackages which need not be hermetically sealed, and may be kept for manymonths without appreciable loss ornlcotine strength, In

practice, double wall paper bags have been entiremixed with water in theusual spray tank in such proportions as are necessary to give therequired strength of nicotine in the spray, usually about 3 lbs. to 100gallons of water. ()wing to the presence of the limited amount ofmineral oil, the spray material does not cake in storage, and is wettedquickly enough for practical ,purposes when stirred with water in thespray tank where it will be rapidly dispersed in fine particles. This isnot the case if too high a percentage of oil is used. It is possiblethat one reason for this rapid dispersion is due to the fact that theoil has a certain fiotative power, but whether this be the trueexplanation or not, his a that the dispersidn o! the spray. material invery iinely-.di-. vided particlesoccurs with great rapidity. I When;applied to a plant,about one-half the nicotine in the spray is presentinsolution, to serve as a contact poison, and this will kill 'manysuckinginsects withwhich-it-makes contact, and also will act as astomach poison until washed away by rain, while remainder of the;nicotine I which is in chemical combination-with the benstats for itsadsorptive properties and not ior its baseexchanseproperties, thecomplex polysilicate still adsorbs its share of the excess alkaloidsalt, but

' because there is less'oi the-"base-exchsnzeoom- Y ple'x'polysilicat'e; relatively, in a given-weight of f spray materiafthanwhen it "is used alonethere' will be a reduced percentace otinsolublealkaloid tonite 'will remain on the .plant even after considerable rain,and whileon the plant will act as is desirable because one applicationor spray destroys the sucking insects and leaves a residue to protectthe plant for a time against chewing insects which may then bethere-orcome somewhat later while the spray deposit remains on the" plant.

Example I! This is an example oi that modification oi the invention inwhich an inert carrier is compounded with the special bentomte-the inertcarrier being a clay which has little or'no base-exchange propertiessuch as would cause a reaction with an alkaloid salt oi the typeemployed in carrying out the invention, but has good adsorptive promrties. By the use of such an inert or substantimly inert carrierintimately mixed with the polymlh onto. it becomes possible to make anadjustment of the relative proportions of soluble and fixed nicotine inthe spray material and therefore in the spray finally produced therefromby the user.

A clay oi the type berelnheiore discussed is 'a stomach poisonto killchewing insects. I I-l -In normal practice such a combination spray ofthe finished product are as follows: 1

salt and a greater percentage of water solu'blealkaloidsaltlntheflnslp'roduct.

In making a spray from the abovespray ma terial it is added to the waterin: in the proportion oi aboutthree 100 gallons. I I II a Example 111*In this example the ilxins com onents ground stems oi flueecured, andtherefore acid, tobacco I The composition of the startins materials I.wet' Dry 4 mm Pounds Special banionite 7'7 moisture 150 140 F tie-curedtobacco dust 6% moisture... 60 .47.

% nicotine sulphate 40% moisture I l 00 co The tobacco dust" usuallycontains about 03% nicotine so that the amount oi nicotine in the aboveproduct; finished. is about 40.3 lbs., or

f nearly 16.3%. I Oi this amount the insoluble comadded to the specialbentonite, such as'has been described hereinbei'ore, the two thoroughlycommlnuted, admixed, as by grinding in a suitable mill, and graded as bysifting in the same way as in Example I, so that th mixture is powderedand will all pass a screen of 100 mesh, or ii de-' sired.- even a finermesh. "To. the powdered material there is added the alkaloid salt andthe .oil and further mixing of th materials is carried out, whereuponthe resulting product is run through a dryer to remove substantially allmoisture; is ground and graded and then the liner material is packagedas desired for storage and shipment. .Thecomposition oi the startingvma-t ,terials and of the finished product is. asiollows: I

plex polysilicate oi nicotine holds about 18 lbs. and the water-solublesalt of nicotine holds about 24.3 lbs. This gives a ratio or about 40%stomach poison and about-% contactpoison, dim'eizarding the nicotine inthe tobacco dust itseltwhich will increase contact poison to aconsiderable extent. I

The amountoi water present during the reac-' tion is about 17 or 18%andin thlsoase-also 5 the product before it enters the dryer ismerelydrye r.

damp and. easily conveyed to and through the The'tobacco dust not onlyserves as a 1' fixing component of :the finished product, but also as afiller to reducecakingduring the drying Wet "Dr Y" I Pound-9 Pouadc 8bentoniife 7% moisture 60 n 46.6 Cay Bancroft) 7%moisture;......-' as26.6 407 cotine sulphate40%moisture.. I 37 22 Lug icsi s L- 5 I a In theoriginal mix the water is about 16%. In this spray material there willbe about 35% bined and about %8ol ilbl e nicotine.

percentage of nicotine in the finished product is about I4.8%,buthecause oi the use o'i'ithe' inert carrier the relative proportiom ofof the'nicotine fixed, thstis, chemically comfixed and-solublenicotinefhave been changed from proportions in Example I. By adjustinstheproportions of the clay with relation to the bentonite, theproportions of the fixed nicotine to the soluble nicotine may becorrespondingly' adjusteq so that's. spray material having a desiredratio oi fixed tosoluble nicotine may be o tained; within certainlimits.

q sallonsoifwaten;

' operation. The tobacco dust also carries a portion of thewater-soluble salt by adsorption or absorption. or both. i

I In using this composltlonto make a spray it isadded to the-water inthe spray tank in'the proportion oi-about three oriour pounds to v lt-is oiten a v l m a as M e-a a ant? I.

The water present during the reaction about 16%. The dry productcontains about 15% nicetine. about two-thirds of which a solubleiand =36pne third insoluble. i

eta-amateurs, the additionof the inert carrier,'which is depended-uponprincipally or tour pounds per v esirable toprovideIaTspray mate-Q ria wi h som p st f m an u u em relatively high in 7 contact poison;vl'ollowing The composition is used in the proportions of about three tofour pounds per 100 gallons oi? water.

Example V A composition in which tannic acid is used as a iixingcomponent may be made as follows:

Wet Dry Pounds Pounds Special bentonite 7% moisture 107 100 40% nicotinesulphate 40% moisture. 45 27 Tannic acid, dry 8 8 Example VI It ispossible to make a durable combination spray composition in which nofixing component is necessary. In such case the water-soluble nicotinesalt should be a salt ota strong monobasic inorganic acid.

While nicotine hydrochloride might be used, in place oi. nicotinesulphate, with a base exchange material, the said nicotine salt being insuch proportions as to provide the necessary excess of nicotine overthat amount which will react with *the base-exchange material, there arecertain dimculties which arise with said nicotine chloride. first,because it is highly hygroscopic and, second, because in general it mayhave a slight injurious effect on many plants, noticeable if repeatedsprays are used. Therefore, to'avoid the hygroscopic effect it is wellto use the salt known as nicotine-zinc-hydrochloride, which is verypermanent. This salt is crystalline and may be said to be dry. The saidsalt usually contains about 47% nicotine, which is non-volatile.

The composition of the mix and of the finished product may be asfollows:

Special bentonito, 1% moisture Nicotine-zinc-hydrochloride Water addedThemixture must be very thoroughly stirred for sufllcient time to insurethe reaction 01' the nicotine with the polysilicate to satisfy thebaseexchange properties of the polysilicate. Usually about 20 minutesare required.

six'pounds of nicotine which during the drying durable and exceedinglyeflective against some insects, it has a place in the art.

It may be used in the proportion of about I three or four pounds to 100gallons of water.

By using a greater proportion of the nicotinezinc-hydrochloride thanthat given in the formula above, a very highly concentrated spraymaterial may be obtained and this is one oi! the principal advantages ofthe said salt.

Also, when making the aqueous spray, soda ash may be added to the extentof about 10 to 12% of the spray composition, by weight. This tends toreduce any danger of injury to the plants.

No special example of a spray composition using oleic acid as a fixingcomponent is given since it may replace any of the other fixingcomponents if used in the same manner and pro portions as the speciallubricating oils hereinbefore described.

It will be seen that the new process necessitates the use of thewater-soluble nicotine salt in much excess, a limitation as to theproportion of water, and, when a di-basic acid is employed, the additionof a fixing component.

Also it will be noted that each product com- I prises a finelycomminuted water-insoluble salt of the stated alkaloid surcharged withan adherent dry water-soluble product carrying the same type of alkaloidin non-volatile form. In the spray material made from a strong monobasicinorganic acid, the said adherent dry product may be merely thewater-soluble mono-basic acid salt of the alkaloid, holding the alkaloidin non-volatile form. In the spray material made sticking of the sprayproducts to the plant, make the use 01' the said ofl in its restrictedproportions, of considerable value.

In usual practice it is customary to add to the water in the spray tanka spreader material. This can be done when using the spray material of'the present invention, it being understood however that such spreadershould be one which has no injurious reaction on the said spray-material. It has been found'that there is a spreader consisting of asulphate of lauryl alcohol, sold on the market under the trade name ofOrvus whichis particularly suitable for use with the spray materials ofthe present invention, and since it is a dry product it may be added tothe spray material at the factory in the proper proportion, which isusually about one-fourth to one per cent by weight of the total sp aymaterial. It has been found that good' tine in substantial excess ofthat necessary to results are attained with 7% lbs. per ton, or

about three-eighths of one per cent.

It'isto be understood that the term fixing component, as used in theclaims designates amaterial selected from the following list 01ingredients in the range of proportions and with the characteristicshereinbetorelstated, namely, (l) tannic acid, (2) flue cured tobaccodust, (3) mineral lubricating oil, (4) oleic acid.

Also it is to be understoodthat the term ."dry

compound of water-soluble non-volatile alkaloid" used in the claimsdesignates either a monobasic acid salt of the relative alkaloid. whichsalt is itself non-volatile, or a poly-basic acid salt 01' the relativealkaloid accompanied by "a fixing component, asdeilned above.

In applicant's Patent No. 2,311,629, dated Feb. 23, 1943'. a diiferentform of spray material using the reaction products of a base-exchangematerial and nicotine is. disclosed but no claim is 2 made in thisapplication to such other spray material or to any process of making it.

What is claimed-is:

1s The process of producing an insecticidal spray material, whichcomprises contacting, in the presence of a limited amount of water notexceedingper, cent and in the presence of a fixing component capable ofmaintaining the alkaloid in non-volatile form, a base-exchange materialhaving adsorptive properties, with a watersoluble salt of an alkaloid,selected from the group consisting of nicotine, nomicotine, anabasine,said salt being provided in an amount sufilcient to supply the alkaloidin substantial excess of that necessary to satisfy the base-exchangepropascasse making aqueous insecticidal combination sprays, comprisingessentially a dry. solid, comminuted base-exchange material in chemicalcombination with an. alkaloid selected fromthe group consisting ofnicotine, nornicotine, and anabasine. and constituting a water-insolublesalt of the alkaloid, said water-insoluble salt carrying an adsorbedadherent dry compound of water-soluble non-volatile alkaloid selectedfrom said group, said adherent dry-compound being material selected fromthe group consisting of; (1) nonvolatile mono-basic acid salts of thesaid alkaloid,

(2) volatile polybasic acid salts of said alkaloid, I.

associated with a fixing component, the proportlon of said water-solublenon-volatile alkaloid in said compound being in appreciable ratiorelative to the amount of alkaloid in the water-insoluble salt. a

5. An insecticidal material suitable for use in 4 alkaloid from the saidpoly-basic acid salt. the

erties of the base-exchange material, and then heatingthe products thusobtained to insure the adsorption of the excess of alkaloid salt by theI base-exchange material and to produce a substantially dry productcarrying both chemically combined fixed alkaloid and uncombined solublesalt of the same alkaloid in non-volatile form.

2. The process of producing an insecticidal spray material whichcomprises mixing, in the presence of a limited amount of water notexceeding 20 per cent, a complex polysilicatehaving base-exchange andadsorptive. properties, nico-' tins sulphate in a proportion containingnicosatisfy the base-exchange properties of the'poly silicate, and notto exceed six per cent of a mineral lubricating oilhaving a viscosityrangamount of alkaloid in said poly-basic acid salt' being inappreciable ratio to the alkaloid iri the water-insoluble salt;

6. An'insecticidal material suitable for use=in making aqueousinsecticidal combination sprays.

comprising essentially a dry, solid. comminuted base-exchange materialin chemical combination with an alkaloid selected from the groupconsisting of nicotine, nornicotine, and anabasine, and constituting awater-insoluble salt of the alkaloid, said water-insoluble salt carryingan adsorbed adherent dry product consisting of a non-volatile 1water-soluble mono-basic acid salt of analkaloid ing between 190 and 900seconds Saybolt at 1005 F., and drying the resultant product.

3. The process of producing an insecticidal spray material, whichcomprises comminglinga complex polysilicate having base-exchange and Iadsorptive properties, and a substantially inert" carrier materialhaving adsorptive properties,

contacting the mixture thus obtained, in the presnot being provided inan amount sufllcient to supply-the alkaloid in substantial excess ofthat necessary to satisfy the base-exchange-properties of thepolysilicate, and then heating the products thus obtainedto insure the.adsorption of the exv e g 1 cess of alkaloid by thepolysilicate and'toproducematerial uit b e" for use in makin 3 aqueous insecticidalcombination sprays, which comprises contacting. in the presence of alimited amount a substantially dry product carrying both chemi- "callycombined fixedalkaloid and uncombined water-solubl salt'of the samealkaloid in nonvolatile'forr'n. 4. An insecticidal material suitable forse in v 4 selected from the aforesaid group.

7. An insecticidal material suitable for use in making aqueousinsecticidal combination sprays, as claimed in claim 6 in which thenon-volatile water-soluble mono-basic acid salt of the alkaloid W is anicotine hydrochloride "salt.

. 8. An insecticidal material suitable for use in making aqueousinsecticidal combination sprays, as claimed in claim 4, in which thefixing component is mineral lubricatin oil having a boilinB point above700 C. and a viscosity of between 180 and 900 seconds Saybolt at 100' R,in a percentage 7 ranging between 2% and 8% by weight of the vinsecticidal material.

9. An insecticidal material suitable for use in making aqueouscombination sprays, as claimedin claim 4, in whichthe fixing componentis fluecured tobacco dust comprising between 20% and by weight of theinsecticidal material.

10. An insecticidal material suitable for use in making aqueouscombination sprays as claimedin claim 4. in which the fixing-componentis tannic acid comprising between 5% and= 10% oi. the insecticidalmaterial.

11. The process of producing. an insecticidal of water, not'exceeding 20per cent, and in the presence or a fixing component, a mixture ofcomminuted solid base-exchange material having adsorptive properties,and a comminuted absorptive inert solid material, with a water-solublepolybasic acid salt 0! an alkaloid selected from the group consisting ofnicotine, nornicotine. anabasine. said salt being provided in an amountsufllcient to supply the alkaloid in substantial excess of thatnecessary to satisfy the base-exchange properties of the base-exchangematerial.

